JPH08797B2 - Process for producing diaminodiphenylmethane compounds - Google Patents
Process for producing diaminodiphenylmethane compoundsInfo
- Publication number
- JPH08797B2 JPH08797B2 JP8988386A JP8988386A JPH08797B2 JP H08797 B2 JPH08797 B2 JP H08797B2 JP 8988386 A JP8988386 A JP 8988386A JP 8988386 A JP8988386 A JP 8988386A JP H08797 B2 JPH08797 B2 JP H08797B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- diaminodiphenylmethane
- formaldehyde
- methyl
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 18
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical class C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 title claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 62
- 150000001448 anilines Chemical class 0.000 claims description 19
- -1 diaminodiphenylmethane compound Chemical class 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 7
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- FICRCFUYRUWRSE-UHFFFAOYSA-N n,n'-bis(2,6-dimethylphenyl)methanediamine Chemical compound CC1=CC=CC(C)=C1NCNC1=C(C)C=CC=C1C FICRCFUYRUWRSE-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 4
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- XJRWMFDPXGJBIC-UHFFFAOYSA-N n,n'-bis[2,6-di(propan-2-yl)phenyl]methanediamine Chemical compound CC(C)C1=CC=CC(C(C)C)=C1NCNC1=C(C(C)C)C=CC=C1C(C)C XJRWMFDPXGJBIC-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OTZUSNPBNWUXCQ-UHFFFAOYSA-N 2-ethyl-6-propan-2-ylaniline Chemical compound CCC1=CC=CC(C(C)C)=C1N OTZUSNPBNWUXCQ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- SFVJGQYZZVZUDN-UHFFFAOYSA-N n,n'-bis(2,6-diethylphenyl)methanediamine Chemical compound CCC1=CC=CC(CC)=C1NCNC1=C(CC)C=CC=C1CC SFVJGQYZZVZUDN-UHFFFAOYSA-N 0.000 description 2
- GIEGUYUSXLKSPV-UHFFFAOYSA-N n,n'-bis(2-methyl-6-propan-2-ylphenyl)methanediamine Chemical compound CC(C)C1=CC=CC(C)=C1NCNC1=C(C)C=CC=C1C(C)C GIEGUYUSXLKSPV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SQMOOVFBFVTTGF-UHFFFAOYSA-N 1-benzyl-1-phenylhydrazine Chemical compound C=1C=CC=CC=1N(N)CC1=CC=CC=C1 SQMOOVFBFVTTGF-UHFFFAOYSA-N 0.000 description 1
- IIXJLIOBJQLEPN-UHFFFAOYSA-N 2,6-dibutylaniline Chemical compound CCCCC1=CC=CC(CCCC)=C1N IIXJLIOBJQLEPN-UHFFFAOYSA-N 0.000 description 1
- WFGHUOGOUOTVBO-UHFFFAOYSA-N 2,6-dipropylaniline Chemical compound CCCC1=CC=CC(CCC)=C1N WFGHUOGOUOTVBO-UHFFFAOYSA-N 0.000 description 1
- VTJGUVJXULLGNA-UHFFFAOYSA-N 2-butyl-6-methylaniline Chemical compound CCCCC1=CC=CC(C)=C1N VTJGUVJXULLGNA-UHFFFAOYSA-N 0.000 description 1
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 description 1
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 description 1
- DDTKYVBFPULMGN-UHFFFAOYSA-N 2-methyl-6-propan-2-ylaniline Chemical compound CC(C)C1=CC=CC(C)=C1N DDTKYVBFPULMGN-UHFFFAOYSA-N 0.000 description 1
- BKJHJIPJEBLCJS-UHFFFAOYSA-N 2-methyl-6-propylaniline Chemical compound CCCC1=CC=CC(C)=C1N BKJHJIPJEBLCJS-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000006413 Prunus persica var. persica Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical class Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- GMKSMTJXIGEYLX-UHFFFAOYSA-N n,n'-bis(2-ethyl-6-methylphenyl)methanediamine Chemical compound CCC1=CC=CC(C)=C1NCNC1=C(C)C=CC=C1CC GMKSMTJXIGEYLX-UHFFFAOYSA-N 0.000 description 1
- FRCFWPVMFJMNDP-UHFFFAOYSA-N n-propan-2-ylaniline Chemical compound CC(C)NC1=CC=CC=C1 FRCFWPVMFJMNDP-UHFFFAOYSA-N 0.000 description 1
- CDZOGLJOFWFVOZ-UHFFFAOYSA-N n-propylaniline Chemical compound CCCNC1=CC=CC=C1 CDZOGLJOFWFVOZ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、2,6−ジアルキル置換アニリン類を酸触媒
の存在下ホルムアルデヒドと反応させて、エポキシ硬化
剤として有用なジフエニルメタン系化合物を製造する方
法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention reacts 2,6-dialkyl-substituted anilines with formaldehyde in the presence of an acid catalyst to produce a diphenylmethane compound useful as an epoxy curing agent. Regarding the method.
2,6−ジアルキル置換アニリンをホルムアルデヒドと
反応させジアミノジフエニルメタン系化合物を製造する
方法は、DE2945614で知られている。A method for reacting 2,6-dialkyl-substituted anilines with formaldehyde to produce diaminodiphenylmethane compounds is known from DE 2945614.
該特許ではホルムアルデヒドと2,6−ジアルキル置換
アニリン類とを酸触媒として蓚酸を用いオートクレーブ
中で、100〜180℃で反応させているが、この方法は生成
物をさらに核水添するための特殊な条件下で行われてい
る反応である。In the patent, formaldehyde and 2,6-dialkyl-substituted anilines are reacted at 100 to 180 ° C in an autoclave using oxalic acid as an acid catalyst, but this method is a special method for further hydrogenating the product. The reaction is carried out under various conditions.
また、2,6ジアルキル置換アニリンの塩酸塩をジエチ
ルカルボネート中でジメチルスルホキサイドを反応させ
て、ジアミノジフエニルメタン系化合物を得る方法もＵ
・Ｓ・Ｐ・4289906で知られている。In addition, a method for obtaining a diaminodiphenylmethane compound by reacting 2,6 dialkyl-substituted aniline hydrochloride with dimethyl sulfoxide in diethyl carbonate is also available.
・ It is known by SP 4289906.
前記のDE2945614の方法はオートクレーブを用いて反
応させるために工業的には有利ではなく、又USP4289906
の方法は収率も低く反応後の操作等を考えると有利な方
法ではない。The above-mentioned method of DE2945614 is not industrially advantageous because it is reacted by using an autoclave, and USP4289906 is used.
The above method is also not advantageous in view of the operation after the reaction because the yield is low.
本発明は工業的に有利であり、また未反応のアニリン
誘導体及びＮ−メチル化合物の混入が極めて少ない高純
度のジアミノジフエニルメタン系化合物の製法を提供し
ようとするものである。The present invention is industrially advantageous and intends to provide a process for producing a high-purity diaminodiphenylmethane-based compound in which unreacted aniline derivative and N-methyl compound are extremely small.
本発明者は鋭意研究を重ねた結果、本発明に達した。
すなわち2,6−ジアルキル置換アニリン類を酸触媒の存
在下ホルムアルデヒドと反応させて、一般式 （式中R1,R2,R3,R4はそれぞれ独立に低級アルキル基を
表わす。） で示されるジアミノジフエニルメタン系化合物を製造
する方法において、2,6−ジアルキル置換アニリン類１
モルに対し0.5〜0.6モルのホルムアルデヒドを室温〜57
℃で添加し、該滴下温度で第１段目の反応を行い、次い
で95〜98℃で第２段目の反応を行うことによりジアミノ
ジフエニルメタン系化合物を工業的に有利に製造できる
ことを見い出した。The present inventor has achieved the present invention as a result of intensive studies.
That is, 2,6-dialkyl-substituted anilines are reacted with formaldehyde in the presence of an acid catalyst to give a compound of the general formula (In the formula, R 1 , R 2 , R 3 and R 4 each independently represent a lower alkyl group.) In the method for producing a diaminodiphenylmethane compound, 2,6-dialkyl-substituted anilines 1
0.5 to 0.6 mol of formaldehyde to room temperature to 57 mol
It was found that a diaminodiphenylmethane compound can be industrially advantageously produced by adding at 0 ° C, carrying out the first step reaction at the dropping temperature, and then carrying out the second step reaction at 95-98 ° C. It was
一般にアニリン誘導体とホルムアルデヒドを反応させ
ると、未反応のアニリン誘導体と副成するＮ−メチル化
合物が、目的物であるジアミノジフエニルメタン系化合
物に混入し、これが硬化剤としての価値を下げる原因に
なっていたが本発明によりこの問題を解決することがで
きた。Generally, when an aniline derivative is reacted with formaldehyde, an unreacted aniline derivative and a by-produced N-methyl compound are mixed into a target compound, a diaminodiphenylmethane compound, which causes a decrease in value as a curing agent. However, the present invention was able to solve this problem.
Ｎ−メチル化合物の副生を抑えるためにはホルムアル
デヒドに対し、2,6−ジアルキル置換アニリン類を過剰
に用いればよいことは推定できるが、この場合、反応後
過剰のアミンを回収除去をする必要があり、工程が長く
なり工業的には有利な方法ではない。そこで芳香族アミ
ンとホルムアルデヒドのモル比について検討を加えた結
果、2,6−ジアルキル置換アニリン類１モルに対し、ホ
ルムアルデヒド0.5〜0.6モル好ましくは0.55〜0.57モル
を使用すると未反応モノアミンが１％以下となり、Ｎ−
メチル化合物はほとんど生成しない事を見い出した。但
し、この場合ホルムアルデヒドの添加温度及び添加後の
反応条件を厳密に守るのが好ましい。例えばホルムアル
デヒドの添加は１〜２時間かけて室温〜57℃、好ましく
は40〜55℃で行う。これより高い温度で添加された場
合、一部Ｎ−メチル化が起る。また、アルデヒドの添加
後は、室温〜57℃で第１段目の反応を行い、次いで１〜
２時間かけて95〜98℃に昇温させて同温度で第２段目の
反応を行う。しかしその後の反応時間が短かい場合は、
反応中間体であるアミノベンジルアニリンの転位が完結
しないため目的物の収率低下の原因となる。2,6−ジア
ルキル置換アニリン類の場合、未置換アニリン又はモノ
置換アニリンと比べ転位速度が遅いため本発明のように
４時間以上好ましくは４〜６時間を必要とする。このよ
うに本発明においてはホルムアルデヒドのモル比と反応
条件とは密接な関係を有している。It can be presumed that an excess amount of 2,6-dialkyl-substituted anilines can be used with respect to formaldehyde in order to suppress the by-product of the N-methyl compound, but in this case, it is necessary to recover and remove the excess amine after the reaction. However, this is not an industrially advantageous method because it requires a long process. Therefore, as a result of investigating the molar ratio of aromatic amine and formaldehyde, when 0.5-0.6 mol of formaldehyde was used per mol of 2,6-dialkyl-substituted aniline, preferably 0.55-0.57 mol, unreacted monoamine was 1% or less. And N-
It was found that almost no methyl compound was formed. However, in this case, it is preferable to strictly observe the addition temperature of formaldehyde and the reaction conditions after the addition. For example, formaldehyde is added at room temperature to 57 ° C., preferably 40 to 55 ° C., for 1 to 2 hours. Partial N-methylation occurs when added at higher temperatures. After the addition of the aldehyde, the first step reaction is performed at room temperature to 57 ° C, and then 1 to
The temperature is raised to 95 to 98 ° C over 2 hours, and the second stage reaction is carried out at the same temperature. However, if the subsequent reaction time is short,
The rearrangement of aminobenzylaniline, which is a reaction intermediate, is not completed, which causes a decrease in the yield of the desired product. In the case of 2,6-dialkyl-substituted anilines, the rearrangement rate is slower than that of unsubstituted aniline or mono-substituted aniline, and therefore 4 hours or more, preferably 4 to 6 hours are required as in the present invention. Thus, in the present invention, there is a close relationship between the molar ratio of formaldehyde and the reaction conditions.
本発明で使用するホルムアルデヒドは、通常37％ホル
マリン水溶液を用いるのが好ましいが、場合によっては
さらに水で希釈して使用してもよい。また酸触媒として
は塩酸又は硫酸を用いるのが好ましく、その使用量は、
2,6−ジアルキル置換アニリン類１モルに対し好ましく
は0.95〜2.2モルの範囲で使用される。The formaldehyde used in the present invention is preferably a 37% aqueous formalin solution, but in some cases, it may be diluted with water before use. It is preferable to use hydrochloric acid or sulfuric acid as the acid catalyst, and the amount used is
It is preferably used in the range of 0.95 to 2.2 mol per mol of the 2,6-dialkyl-substituted aniline.
次に本発明で使用する2,6−ジアルキル置換アニリン
類の具体例としては、例えば2,6−ジメチルアニリン、
2,6−ジエチルアニリン、２−メチル、６−エチルアニ
リン、2,6−ジプロピルアニリン、2,6−ジイソプロピル
アニリン、2,6−ジブチルアニリン、２−メチル−６−
イソプロピルアニリン、２−メチル−６−プロピルアニ
リン、２−エチル−６−イソプロピルアニリン、２−エ
チル−６−イソプロピルアニリン等があげられる。Next, specific examples of the 2,6-dialkyl-substituted anilines used in the present invention include, for example, 2,6-dimethylaniline,
2,6-diethylaniline, 2-methyl, 6-ethylaniline, 2,6-dipropylaniline, 2,6-diisopropylaniline, 2,6-dibutylaniline, 2-methyl-6-
Examples thereof include isopropylaniline, 2-methyl-6-propylaniline, 2-ethyl-6-isopropylaniline and 2-ethyl-6-isopropylaniline.
これらの2,6−ジアルキル置換アニリン類は１種又は
２種以上を任意の比率で混合して用いてもよく、１種の
2,6−ジアルキル置換アニリンを用いた場合、対称形
の、また２種以上を用いた場合、対称形及び非対称形の
混合物を与える。These 2,6-dialkyl-substituted anilines may be used either individually or in combination of two or more, at any ratio.
The use of 2,6-dialkyl-substituted anilines gives symmetrical mixtures, and the use of more than one gives symmetrical and asymmetrical mixtures.
本発明により得られる一般式（１）で示される化合物
の具体例は、メチレンビス（2,6−ジメチルアニリ
ン）、メチレンビス（2,6−ジエチルアニリン）、メチ
レンビス（2,6−ジプロピルアニリン）、メチレンビス
（2,6−ジイソプロピルアニリン）、メチレンビス（2,6
−ジブチルアニリン）、メチレンビス（２−メチル−６
−エチルアニリン）、メチレンビス（２−メチル−６−
プロピルアニリン）、メチレンビス（２−メチル−６−
イソプロピルアニリン）、メチレンビス（２−メチル−
６−ブチルアニリン）、メチレンビス（２−エチル−６
−イソプロピルアニリン）、メチレンビス（２−エチル
−６−プロピルアニリン）等である。Specific examples of the compound represented by the general formula (1) obtained by the present invention include methylenebis (2,6-dimethylaniline), methylenebis (2,6-diethylaniline), methylenebis (2,6-dipropylaniline), Methylenebis (2,6-diisopropylaniline), methylenebis (2,6
-Dibutylaniline), methylenebis (2-methyl-6)
-Ethylaniline), methylenebis (2-methyl-6-)
Propylaniline), methylenebis (2-methyl-6-
Isopropylaniline), methylenebis (2-methyl-)
6-butylaniline), methylenebis (2-ethyl-6)
-Isopropylaniline), methylenebis (2-ethyl-6-propylaniline) and the like.
さらに２種以上の2,6−ジ置換アニリン類を用いた場
合の主成分である非対称形の化合物の具体例は、 2,6−ジメチル−２′,6′−ジエチル−4,4′−ジアミ
ノジフエニルメタン 2,6−ジメチル−２′,6′−ジイソプロピル−4,4′−
ジアミノジフエニルメタン 2,6−ジメチル−２′,6′−ジプロピル−4,4′−ジア
ミノジフエニルメタン 2,6−ジメチル−２′,6′−ジブチル−4,4′−ジアミ
ノジフエニルメタン 2,6−ジエチル−２′,6′−ジイソプロピル−4,4′−
ジアミノジフエニルメタン 2,6−ジエチル２′,6′−ジプロピル−4,4′−ジアミ
ノジフエニルメタン 2,6−ジエチル−２′,6′−ジブチル−4,4′−ジアミ
ノジフエニルメタン ２−メチル−６−エチル−２′,6′−ジエチル−−4,
4′−ジアミノジフエニルメタン ２−メチル−６−エチル２′,6′−ジイソプロピル−
4,4′−ジアミノジフエニルメタン ２−メチル−６−イソプロピル−２′,6′−ジエチル
−4,4′−ジアミノジフエニルメタン ２−メチル−６−イソプロピル−２′,6′−ジイソプ
ロピル−4,4′−ジアミノジフエニルメタン ２−メチル−６−エチル−２′−メチル−６′−イソ
プロピル−4,4′−ジアミノジフエニルメタン ２−メチル−６−エチル−２′−エチル−６′−イソ
プロピル−4,4′−ジアミノジフエニルメタン 等であるが、これらに限定されるものではない。Further, specific examples of the asymmetric compound which is the main component when two or more 2,6-disubstituted anilines are used are 2,6-dimethyl-2 ', 6'-diethyl-4,4'- Diaminodiphenylmethane 2,6-dimethyl-2 ', 6'-diisopropyl-4,4'-
Diaminodiphenylmethane 2,6-dimethyl-2 ', 6'-dipropyl-4,4'-diaminodiphenylmethane 2,6-dimethyl-2', 6'-dibutyl-4,4'-diaminodiphenylmethane 2,6-diethyl-2 ', 6'-diisopropyl-4,4'-
Diaminodiphenylmethane 2,6-diethyl 2 ', 6'-dipropyl-4,4'-diaminodiphenylmethane 2,6-diethyl-2', 6'-dibutyl-4,4'-diaminodiphenylmethane 2 -Methyl-6-ethyl-2 ', 6'-diethyl-4-,
4'-diaminodiphenylmethane 2-methyl-6-ethyl 2 ', 6'-diisopropyl-
4,4'-Diaminodiphenylmethane 2-methyl-6-isopropyl-2 ', 6'-diethyl-4,4'-diaminodiphenylmethane 2-methyl-6-isopropyl-2', 6'-diisopropyl- 4,4'-Diaminodiphenylmethane 2-methyl-6-ethyl-2'-methyl-6'-isopropyl-4,4'-diaminodiphenylmethane 2-methyl-6-ethyl-2'-ethyl-6 Examples include, but are not limited to, '-isopropyl-4,4'-diaminodiphenylmethane.
本発明の方法によれば反応終了後、反応液又は塩酸塩
結晶を苛性ソーダ、アンモニア水、又はソーダ灰等のア
ルカリで中和し、水洗、乾燥又は水分除去するだけで未
反応のモノアミンが１％以下でさらにＮ−メチル化合物
をほとんど含有しないジアミノフエニルメタン系化合物
が得られ、これを用いることにより高純度のエポキシ用
硬化剤を製造することが出来る。According to the method of the present invention, after completion of the reaction, the reaction solution or the hydrochloride crystals are neutralized with an alkali such as caustic soda, ammonia water, or soda ash, and washed with water, dried or removed of water to obtain 1% of unreacted monoamine. In the following, a diaminophenylmethane compound containing almost no N-methyl compound is obtained, and by using this, a high-purity epoxy curing agent can be produced.
以下に実施例をあげて本発明をさらに詳しく説明す
る。Hereinafter, the present invention will be described in more detail with reference to examples.
実施例1. 10４つ口コルベンに水2400gを加え撹拌下36％塩酸1
200g（11.85モル）を加える。次いで2,6−キシリジン71
6g（5.91モル）を55℃以下で滴下した。次に37％ホルマ
リン水溶液263.6g（3.25モル）を50℃〜55℃の温度を保
ちながら１時間を要して滴下した後、同温度で２時間反
応させ、次いで２時間を要して直線的に95℃まで昇温し
同温度で５時間反応させた。得られた反応スラリー液を
40℃に冷却して20％苛性ソーダ2370g（11.85モル）を２
時間を要して滴下中和した後、過し、硝酸銀でテスト
して塩素イオンが検出されなくなるまで水洗をくり返し
た後乾燥し、黄白色結晶を得た。メチレンビス（2,6−
ジメチルアニリン）は1500g（粗収率99.9％）であっ
た、またガスクロマトグラフィーによる分析の結果、メ
チレンビス（2,6−ジメチルアニリン）の純度99.2％
で、未反応の2,6−キシリジンの含有量は0.8％であり、
またＮ−メチル化合物は検出されなかった。Example 1. 2400 g of water was added to 10-necked Kolben and 36% hydrochloric acid was added with stirring 1
200 g (11.85 mol) are added. Then 2,6-xylidine 71
6 g (5.91 mol) was added dropwise at 55 ° C or lower. Next, 263.6 g (3.25 mol) of 37% formalin aqueous solution was added dropwise over 1 hour while maintaining the temperature of 50 ° C to 55 ° C, followed by reacting for 2 hours at the same temperature and then linearly over 2 hours. The temperature was raised to 95 ° C and the reaction was carried out at the same temperature for 5 hours. The obtained reaction slurry liquid
Cool to 40 ° C and add 2370 g (11.85 mol) of 20% caustic soda to 2
After dripping and neutralizing for a long time, the mixture was passed, and the mixture was passed through a test with silver nitrate, washed repeatedly with water until chlorine ions were not detected, and then dried to obtain yellowish white crystals. Methylenebis (2,6-
Dimethylaniline) was 1500 g (crude yield 99.9%), and as a result of analysis by gas chromatography, the purity of methylenebis (2,6-dimethylaniline) was 99.2%.
The content of unreacted 2,6-xylidine is 0.8%,
N-methyl compound was not detected.
注） Ｎ−メチル化合物 比較例1. 実施例１の方法において、ホルマリン水溶液の滴下温
度を65℃とし、ホルマリン水溶液滴下後の同温度での反
応時間を20分とし、さらに95℃までの昇温を20分に短縮
し、昇温後の反応時間にして他は実施例１と同様の操作
で淡褐色の結晶1413gを得た（粗収率94％）。得られた
メチレンビス（2,6−ジメチルアニリン）をガスクロマ
トグラフィーで分析した結果、 メチレンビス（2,6−ジメチルアニリン） ……91.6％ 未反応モノアミン〔2,6−キシリジン〕 ……6.0％ Ｎ−メチル化合物 ……2.4％ の組成であった。Note) N-methyl compound Comparative Example 1. In the method of Example 1, the dropping temperature of the formalin aqueous solution was set to 65 ° C., the reaction time at the same temperature after dropping the formalin aqueous solution was set to 20 minutes, and the temperature rise to 95 ° C. was shortened to 20 minutes. 1413 g of light brown crystals were obtained by the same procedure as in Example 1 except that the reaction time after heating was raised (crude yield 94%). The obtained methylenebis (2,6-dimethylaniline) was analyzed by gas chromatography. As a result, methylenebis (2,6-dimethylaniline) …… 91.6% unreacted monoamine [2,6-xylidine] …… 6.0% N- Methyl compound: Composition was 2.4%.
実施例2. 10４つ口コルベンに水1960gと36％塩酸980g（9.68
モル）を加え、次いで2,6−ジエチルアニリン720g（4.8
3モル）を50〜55℃を保ちながら滴下した。得られた白
色スラリー液を52℃〜54℃を保ちながら37％ホルマリン
水溶液223.2g（2.75モル）を1.5時間で滴下した後、同
温度で２時間反応した後、1.5時間を要して95℃まで昇
温した。そして95〜98℃で６時間反応を行った後40℃ま
で冷却し20％苛性ソーダ1936g（9.68モル）で中和した
実施例１と同様過水洗、乾燥を行い、白桃色の結晶14
95gを得た（粗収率99.8％）。ガスクロマトグラフィー
による分析の結果、メチレンビス（2,6−ジエチルアニ
リン）99.45％、未反応の2,6−ジエチルアニリン0.55
％、Ｎ−メチル化合物はトレースであった。Example 2. In a four-necked Kolben, 1960 g of water and 980 g of 36% hydrochloric acid (9.68
Mol) and then 720 g (4.8%) of 2,6-diethylaniline.
3 mol) was added dropwise while maintaining 50 to 55 ° C. 223.2 g (2.75 mol) of 37% formalin aqueous solution was added dropwise over 1.5 hours while maintaining the obtained white slurry liquid at 52 ° C to 54 ° C, and after reacting at the same temperature for 2 hours, it took 1.5 hours to reach 95 ° C. The temperature was raised to. Then, the mixture was reacted at 95 to 98 ° C. for 6 hours, cooled to 40 ° C., neutralized with 20% caustic soda 1936 g (9.68 mol), washed with water and dried in the same manner as in Example 1 to give white peach crystals 14
95g was obtained (crude yield 99.8%). As a result of analysis by gas chromatography, methylenebis (2,6-diethylaniline) 99.45%, unreacted 2,6-diethylaniline 0.55
%, N-methyl compound was trace.
実施例3. ２４つ口コルベンに水800g、2,6−ジイソプロピル
アニリン177g（1.0モル）を加え、次いで36％塩酸101.4
g（1.0モル）を１時間を要して滴下した。次に40〜45℃
を保ちながら37％ホルマリン水溶液46.2g（0.57モル）
を１時間を要して滴下した後、同温度で１時間反応した
後２時間を要して95℃まで昇温した。そしてさらに５時
間同温度で反応を行った後、25％アンモニア水140.5gを
同程度で徐々に滴下し中和した。アンモニア水を滴下し
た後１時間同温度で撹拌した後オイル層を分液、水洗、
水分カットして褐色液体180gを得た（粗収率98.4％）。
ガスクロマトグラフィーの分析の結果、メチレンビス
（2,6−ジイソプロピルアニリン）96.3％、原料に依存
する異性体2.9％、未反応2,6−ジイソプロピルアニリン
（異性体を含む）0.7％、Ｎ−メチル化合物0.1％であっ
た。Example 3. To a 4-necked Kolben, 800 g of water and 177 g (1.0 mol) of 2,6-diisopropylaniline were added, followed by 36% hydrochloric acid 101.4.
g (1.0 mol) was added dropwise over 1 hour. Then 40-45 ℃
Keeping the same, 37% formalin aqueous solution 46.2g (0.57mol)
Was added dropwise over 1 hour, the mixture was reacted at the same temperature for 1 hour, and then heated up to 95 ° C over 2 hours. After reacting for 5 hours at the same temperature, 140.5 g of 25% ammonia water was gradually added dropwise at the same degree to neutralize. After adding ammonia water dropwise and stirring for 1 hour at the same temperature, the oil layer was separated, washed with water,
The water was removed to obtain 180 g of a brown liquid (crude yield 98.4%).
As a result of analysis by gas chromatography, methylenebis (2,6-diisopropylaniline) 96.3%, raw material-dependent isomer 2.9%, unreacted 2,6-diisopropylaniline (including isomer) 0.7%, N-methyl compound It was 0.1%.
実施例4. 実施例３で使用した2,6−ジイソプロピルアニリン177
gの代りに2,6−ジメチルアニリン72.7g（0.6モル）と2.
6−ジイソプロピルアニリン70.8g（0.4モル）を用い、
他は実施例３とまったく同様にして褐色液体154g（粗収
率99％）を得た。ガスクロマトグラフィーによる分析の
結果、組成は次の様であった。（原料に起因する異性体
は無視した） メチレンビス（2,6−ジメチルアニリン） ……36.6％ メチレンビス（2,6−ジイソプロピルアニリン）……15.
6％ 2,6−ジメチル−２′,6′−ジイソプロピル−4,4′−ジ
アミノジフエニルメタン ……48.0％ Ｎ−エチル化合物は0.1％以下であった。Example 4. 2,6-Diisopropylaniline 177 used in Example 3
72.7 g (0.6 mol) of 2,6-dimethylaniline instead of g and 2.
Using 70.8 g (0.4 mol) of 6-diisopropylaniline,
Otherwise in the same manner as in Example 3, 154 g of a brown liquid (crude yield 99%) was obtained. As a result of analysis by gas chromatography, the composition was as follows. (Ignored isomers due to raw materials) Methylenebis (2,6-dimethylaniline) …… 36.6% Methylenebis (2,6-diisopropylaniline) …… 15.
6% 2,6-Dimethyl-2 ', 6'-diisopropyl-4,4'-diaminodiphenylmethane ...... 48.0% The N-ethyl compound content was 0.1% or less.
実施例5. 実施例３で使用した2,6−ジイソプロピルアニリン177
gの代りに２−メチル−６−エチルアニリン81g（0.6モ
ル）と２−メチル−６−イソプロピルアニリン59.6g
（0.4モル）を用い他は実施例３とまったく同様にして
褐色液体150.0gを得た（粗収率98.3％）。ガスクロマト
グラフィーによる分析の結果、以下の組成であった。Example 5. 2,6-Diisopropylaniline 177 used in Example 3
81 g (0.6 mol) of 2-methyl-6-ethylaniline and 59.6 g of 2-methyl-6-isopropylaniline instead of g
150.0 g of a brown liquid was obtained in the same manner as in Example 3 except that (0.4 mol) was used (crude yield 98.3%). As a result of analysis by gas chromatography, the composition was as follows.
メチレンビス（２−メチル−６−エチルアニリン）38
％ メチレンビス（２−メチル−６−イソプロピルアニリ
ン） 18 ％ 2,2′−ジメチル−６−エチル−６′−イソプロピル−
4,4′−ジアミノジフエニルメタン 43.0％ Ｎ−メチル化合物 0.2％ 実施例6. ２４つ口フラスコに2,6−ジメチルアニリン40.0g
（0.33モル）、2,6−ジエチルアニリン49.2g（0.33モ
ル）、2,6−ジイソプロピルアニリン58.4g（0.33モル）
と水800gを加え撹拌下36％塩酸101.4g（1.0モル）を加
え、50℃に調整した後、37％ホルマリン水溶液45.4g
（0.56モル）を１時間を要して滴下した後、同温度で２
時間反応させた後、1.5時間を要して98℃まで昇温し
た。同温度で６時間反応させた後、25％アンモニア水14
0.5gを95〜98℃で滴下中和した。中和後１時間撹拌して
オイル層が中性になっていることを確認した後、オイル
分離して２の水で３回水洗した後、減圧下水分カット
を行った。Methylenebis (2-methyl-6-ethylaniline) 38
% Methylenebis (2-methyl-6-isopropylaniline) 18% 2,2'-Dimethyl-6-ethyl-6'-isopropyl-
4,4'-Diaminodiphenylmethane 43.0% N-Methyl compound 0.2% Example 6. 20.0-dimethylaniline 40.0 g in a 24-neck flask
(0.33 mol), 2,6-diethylaniline 49.2 g (0.33 mol), 2,6-diisopropylaniline 58.4 g (0.33 mol)
And water (800 g) are added, 36% hydrochloric acid (101.4 g, 1.0 mol) is added with stirring, and the temperature is adjusted to 50 ° C., followed by 37% formalin aqueous solution (45.4 g).
(0.56 mol) was added dropwise over 1 hour, and then 2 at the same temperature.
After reacting for an hour, the temperature was raised to 98 ° C. over 1.5 hours. After reacting at the same temperature for 6 hours, 25% ammonia water 14
0.5g was neutralized dropwise at 95-98 ° C. After neutralization, the mixture was stirred for 1 hour, and after confirming that the oil layer was neutral, the oil was separated, washed with water of 2 times 3 times, and then water cut under reduced pressure.
得られた生成物159.6g（粗収率99％）をガスクロマトグ
ラフィーで分析した結果、未反応モノアミン（上記３成
分のアミン）は0.6％であった、残りは６成分からなる
目的物であった。（ガスクロマトグラフィーで完全に分
離されてないため組成及びＮ−メチル化合物は不明であ
る）As a result of gas chromatography analysis of the obtained product (159.6 g, crude yield 99%), the unreacted monoamine (the above-mentioned three-component amine) was 0.6%, and the rest was the target product consisting of six components. It was (The composition and N-methyl compound are unknown because they are not completely separated by gas chromatography)
Claims (4)
の存在下ホルムアルデヒドと反応させて一般式 （式中R1.R2.R3.R4はそれぞれ独立に低級アルキル基を
表わす。） で示されるジアミノジフェニルメタン系化合物を製造す
る方法において、2,6−ジアルキル置換アニリン類１モ
ルに対し0.5〜0.6モルのホルムアルデヒドを室温〜57℃
で添加し、該滴下温度で第１段目の反応を行い、次いで
95〜98℃で第２段目の反応を行うことを特徴とするジア
ミノジフェニルメタン系化合物の製法。1. A general formula for reacting 2,6-dialkyl-substituted anilines with formaldehyde in the presence of an acid catalyst. (In the formula, R 1 .R 2 .R 3 .R 4 each independently represents a lower alkyl group.) In the method for producing a diaminodiphenylmethane compound, 0.5 ~ 0.6 mol formaldehyde at room temperature ~ 57 ℃
The reaction in the first stage was carried out at the dropping temperature, and then
A process for producing a diaminodiphenylmethane-based compound, which comprises performing the second step reaction at 95 to 98 ° C.
キル置換アニリン１モルに対し0.55〜0.57モルであり、
ホルムアルデヒド添加後95〜98℃で４時間以上反応させ
る特許請求の範囲第（１）項の方法。2. The amount of formaldehyde used is 0.55 to 0.57 mol per 1 mol of the 2,6-dialkyl-substituted aniline,
The method according to claim (1), wherein the reaction is carried out at 95 to 98 ° C. for 4 hours or more after the addition of formaldehyde.
ら55℃の温度で添加する特許請求の範囲第（２）項の方
法。3. The method according to claim 2, wherein formaldehyde is added at a temperature of 40 to 55 ° C. over 1 to 2 hours.
ニリン１モルに対し0.9〜2.2モルである特許請求の範囲
第（１），（２）又は（３）項の方法。4. The method according to claim 1, wherein the amount of the acid catalyst used is 0.9 to 2.2 mol per mol of the 2,6-dialkyl-substituted aniline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8988386A JPH08797B2 (en) | 1986-04-21 | 1986-04-21 | Process for producing diaminodiphenylmethane compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8988386A JPH08797B2 (en) | 1986-04-21 | 1986-04-21 | Process for producing diaminodiphenylmethane compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62249946A JPS62249946A (en) | 1987-10-30 |
| JPH08797B2 true JPH08797B2 (en) | 1996-01-10 |
Family
ID=13983161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8988386A Expired - Lifetime JPH08797B2 (en) | 1986-04-21 | 1986-04-21 | Process for producing diaminodiphenylmethane compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08797B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2427593T3 (en) * | 2007-01-08 | 2013-10-31 | Basf Se | Procedure for obtaining diphenylmethanediamine |
| US8466320B2 (en) * | 2007-06-12 | 2013-06-18 | Basf Se | Method for the recovery of mineral acids from saline solutions |
| CN101250114B (en) | 2008-03-24 | 2010-11-03 | 周建 | Method for manufacturing 3-chlorin-3'-ethyl-4,4'-diaminodiphenylmethane |
| CN114716322B (en) * | 2022-03-15 | 2024-02-23 | 安徽兴东化工有限公司 | A preparation process and system for 4,4′-methylenebis(2-methyl-6-ethylaniline) |
-
1986
- 1986-04-21 JP JP8988386A patent/JPH08797B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62249946A (en) | 1987-10-30 |
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